Process for the preparation of monocyclic ketones and their alkyl derivatives havingmore than nine ring members



Patented Feb. 1 9, 1929.

UNITED- STATES,

PATENT OFFICE.

LEOIOLD RUZICKA, OF GENEVA, SWITZERLAND, ASSIGNOR TO 'M. NAEF & CO., 0]?

' GENEVA, SWITZERLAND, COMPANY OF SWITZERLAND.

PROCESS FOR THE PREPARATION OF MONOCY CLIC KETONES AND THEIR ALKYLgDE- -RIVATIVESHAVING MORE THAN NINE RING MEMBERS.

1N0 Drawing. Application filed November 19, 1926, Serial No. 149,534, and in Switzerland Dec mber In the prior application Serial No. 36,049

filed June 9, 1925, there is described a process of preparing monocyclic ketones having more than nine ring members, which comprises heating a "normal straight chain aliphatic dicarboxylic acid salt of the fourth group of the periodic system especially thorium and cerium, said acid having a carbon chain containing more than ten carbon atoms, the carboxylic acid groups being linked to the end carbons thereof. p I

It has also been discovered that in a general manner for the preparation of monocyclic ketones having more than nine ring members and of their alkyl derivatives, from the dicarboxylic acids having more than ten carbon atoms in a normal chain or from their alkyl derivatives, themetals and the compounds of metals belonging to the fourth group of the periodic system may advantageously be employed.

According to the present invention zirco- I nium whichv belongs to the said metals, or its.

compounds such as for instance zirconium oxide are employedeither alone or mixed with another metal or metal compound belonging to the said fourth group ofthe periodic system.

It is also'advantageous to use a mixturev of several metals of the third grou of the periodic system or of the rare eart s, these mixtures being obtained artificially or otherwise.

Mixtures of the above mentioned dicarboxylic acids or their alkyl derivatives, pre- .The pure 3-methyl-cyclopentadecanone Example 2. 8-methyl tetradecane 1.14. dicarboxylic ketones, it is possible to directly heat the acids or .the acid'anhydrides alone or in presence of metals or-metal compounds, at a comparatively high temperature,,instead of first transforming the corresponding dicarboxylic acids into salts. In this case the use of metals of the fourth group of the periodic system is also advantageous.

The ketones of their alkyl derivatives ob- 1 tained by the described process can be used as perfumes or as primary materials for'the preparation of other technically important compounds.

E maimple- 1.

erably in a vacuum, up to a temperature of 390? C. to 500 degrees centigrade and the distillate obtained therefrom is worked up by fractional distillation. The fractions dis-.

C0 ZIO: 2002 acid is heated upto above 300 to 500 degrees centigrade and towards the end of the re- The zirconium salt of 3-methyl-tetradecane-llt-dicarboxylic acid isheated, pref action preferably in a vacuum with zirconium hydroxide in a quantity which does not sufficeifor completely converting the acid into the normal salt. The product obtained-- istreate-d according to the method described in Example 1. v I

Example 5.

A mixture of the zirconium and thorium salts of 4-methyl-tetradecane-1.l-dicarboxylie acid is heated and worked up as described Emample a methyl tetradecane 1.14 dicarboxylic acid is heated at about 300 to 500 C. and towards the end of the react-ion preferably in a vacuum, with zirconium oxide. The product obtained is worked up as described in Example 3.

E amnple 5.

The zirconium salt of tetradecane-1.14-dicarboxyhc acid is heated and worked up as described. in Example 1. The cyclo-pentadecanone is obtained which distills at about 120 C. (at 0.3 mm.) and melts at 63 C.

E a'ample 6.

Tetradecane-1.14l-dicarboxylic acid is heat ed at about 300 to 500 C. towards the end of the reaction preferably in vacuum, with zirconium hydroxide. The distillate resulting therefrom is Worked up as described in Example 5.

Ewample '7.

3 methyl tetradecane 1.14 dicarlooxylic acid is heated to about 300 to 500 C. towards the end of the reaction preferably in a vacuum. The distillate which results therefrom is worked up as described in example 5.

E :eample 8.

The anhydride of tetradecane-1.1 l-dicarboxylic acid is heated to about 300 to 500 C. towards the end of the reaction preferably in a vacuum with zirconium hydroxide and worked up as described in Example 5.

' Example .9.

The anhydride of etinetl1yl-tetradecane- I lll-dicarboxylic acid is heated to about 300 to 500 C. towards the end of the reaction preferably in a vacuum with zirconium hydroxide and Worked up as described in Example 5.

. Example 10.

A zirconium salt of tetradecane-lll-dicarboxylic acid which has been prepared by adding zirconium nitrate to the solution of the sodium-salt of this acid in a quantity which does not sutlice for completely converting the acid into the normal salt, is heated and worked up as described in Example 1.

Example 11.

The zirconium salt of octzidecane-LlS-dicarboxylic acid is heated preferably in a vacuum to about 300 to 500 C. and the resulting distillate is worked up by fractional distillation. The fraction distilling at from 140 to 180 C. (at 0.3 mm.) is then treated with semicarbazide or other reagent usually employed for isolating the ketones. The cyclononadecanone in a pure state can in this manner be isolated by treating the semicarbazone purified by crystallization from alcohol, and melting at 184 C. This ketone boils at 160 C. (at 0.3 mm.), melts at 72 C. and has a smell which nearly corresponds to that of civetone. It can'therefore be used as a perfume and as an intermediate for preparing other interesting technical compounds; by oxidizing the cyclononadecanone with chromic acid heptadecane-l.17-diearboxylic acid is formed. E wample 12.

A mixture of cyclopentadecanone and cyclohexadecanone is obtained by working up according to the method described in Exampie 1 a mixture of zirconium and lanthanum salts of tetr'adecane-l.l l-dicarbolic and pentadecane-l.l5-dicarboxylic acid.

I claim:

1. A process for the preparation of monocyclic ketones having more'than nine ring members comprising heating zirconium salts of polyinethylene dicarboxylic' acids, having more than ten carbon atoms in a normal chain the carboxylic acid groups being linked to the end carbons thereof. I

2. A process for the preparation of monocyclic ketones having more than nine ring members comprising heating a mixture of polymethylene dicarboxylic acid salts of metals belonging to the fourth group of the periodic system having more than ten carbon atoms in a normal chain the carboxylic acid groups being linked to the end carbons 1 acid groups being linked to the end carbons thereof. a

In testimony whereof I afiix my signature.

LEOPOLD RUZIOKA. 

